Transparent electroconductive film and process for producing same

ABSTRACT

There are provided: 
     (1) a process for producing an InSbO 4 -containing transparent electroconductive film, which comprises the step of sputtering simultaneously: 
     (i) a target (A) for sputtering, which comprises In, Sb and O, and whose atomic ratio of Sb/In is from 0.9 to 1.1, and 
     (ii) a target (B) for sputtering, which comprises Sb, 
     (2) a transparent eletroconductive film, which contains In, Sb and O, and whose atomic ratio of Sb/In is from 0.8 to 1.5, and 
     (3) a target for sputtering, which contains In, Sb and O, and whose atomic ratio of Sb/In is from 1.2 to 2.0.

FIELD OF THE INVENTION

The present invention relates to a transparent electroconductive filmand a process for producing the same.

BACKGROUND OF THE INVENTION

Transparent electroconductive films are used for applications such aselectrodes for inorganic EL panels, liquid crystal displays and solarbatteries; hot wave reflection films for window glass; and antistaticfilms. Among the transparent conductive films, an indium-tin oxide filmcomprising an indium oxide containing 2 to 20% by weight of tin oxidehas many applications because of its high electroconductivity (that is,low electric resistivity) and superior translucency. The “indium-tinoxide” is hereinafter referred to as ITO.

However, the ITO has problems that (1) it is expensive, because itcontains an expensive indium oxide in an amount of from 80 to 98% byweight, and (2) its transparency is not good, because it absorbs lightranging from visible rays having short wave lengths to ultraviolet rays.

In the production of inorganic EL panels, it is required to use atransparent electroconductive film, which does not decrease itselectroconductivity even when heat-treated in air at a temperatureexceeding 800° C. However, a transparent electroconductive filmcomprising the ITO, which is usually used for the production ofinorganic EL panels, has a problem that it decreases itselectroconductivity when heat-treated under such conditions.

As one of transparent electroconductive materials substitutable for theITO, InSbO₄ is proposed. Said InSbO₄ has characteristics that (1) it ischeaper than the ITO, because a content of the expensive indium oxide isonly a half of that of the ITO on a weight basis, and (2) itstransparency is superior to the ITO, because it absorbs little lightranging from visible rays having short wave lengths to ultraviolet rays.However, an InSbO₄-containing transparent electroconductive film hasnever been obtained. For example, JP-A 9-71419 discloses a process forproducing an InSbO₄-containing sintered object comprising the steps of(i) shaping a mixed powder of an indium oxide powder and an antimonyoxide powder to obtain a shaped product, and (ii) sintering the shapedproduct: however, it discloses no InSbO₄-containing transparentelectroconductive film.

SUMMARY OF THE INVENTION

An object of the present invention is to provide a process for producingan InSbO₄-containing transparent eletroconductive film having a highelectroconductivity and a superior transparency.

Another object of the present invention is to provide a process forproducing a transparent electroconductive film exhibiting littledecrease in electroconductivity even when heat-treated at a hightemperature.

The present inventors have found a problem that a film obtained bysputtering a target (A) for sputtering, which target contains In, Sb andO, and whose atomic ratio of Sb/In is from 0.9 to 1.1, contains a largeamount of In dramatically departing from a stoichimetric ratio ofInSbO₄, and as a result, a film having a high conductivity cannot beobtained.

The present inventors have undertaken extensive studies to solve such aproblem, and as a result, have found that:

(1) there can be obtained an InSbO₄-containing transparentelectroconductive film, whose atomic ratio of In and Sb is near to thestoichimetric ratio of InSbO₄ and which has a high electroconductivity,by sputtering simultaneously the above-mentioned target (A) forsputtering and a metal Sb-containing target (B) for sputtering, and

(2) there can be obtained an InSbO₄-containing transparentelectroconductive film, wherein Sn and/or Hf is doped, whose atomicratio of In and Sb is near to the stoichimetric ratio of InSbO₄, andwhich has a high electroconductivity, (a) by sputtering simultaneouslythe target (A) for sputtering, the target (B) for sputtering and atleast one target (C) for sputtering selected from the group consistingof Sn, SnO₂, Hf and HfO₂; or (b) by sputtering simultaneously a target(D) for sputtering, which contains In, Sb, O and at least one elementselected from the group consisting of Sn and Hf, and whose atomic ratioof Sb/In is from 0.9 to 1.1, and the target (B) for sputtering. Thereby,the present invention has been obtained.

Further, the present inventors have found that:

(1) a transparent film, which has high electroconductivity, whichexhibits little decrease in electroconductivity even when heat-treatedat a high temperature, and which contains In, Sb and O in a specificproportion, can be obtained by sputtering simultaneously the target (A)for sputtering and the target (B) for sputtering,

(2) a transparent film, which has high electroconductivity, whichexhibits little decrease in electroconductivity even when heat-treatedat a high temperature, and which contains In, Sb and O in a specificproportion, can be obtained by sputtering simultaneously the target (A)for sputtering, the target (B) for sputtering and the target (C) forsputtering,

(3) a target for sputtering, which contains In, Sb and O, and which hasa specific atomic ratio of Sb/In can accomplish the objects of thepresent invention,

(4) a target for sputtering, which contains In, Sb, O and at least oneelement selected from the group consisting of Sn and Hf, and which has aspecific atomic ratio of Sb/In can accomplish the objects of the presentinvention,

(5) there can be obtained an InSbO₄-containing transparentelectroconductive film by sputtering a target (E) for sputtering, whichcontains In, Sb and O, and which has a specific atomic ratio of Sb/In,

(6) there can be obtained an InSbO₄-containing transparentelectroconductive film by sputtering simultaneously the target (3) forsputtering and at least one target (C) for sputtering, and

(7) there can be obtained an InSbO₄-containing transparentelectroconductive film by sputtering a target (F) for sputtering, whichcontains In, Sb, O and at least one element selected from the groupconsisting Sn and Hf, and which has a specific atomic ratio of Sb/In.

Thereby, the present invention has been obtained.

The present invention provides:

(1) a process for producing an InSbO₄-containing transparentelectroconductive film, which comprises the step of sputteringsimultaneously:

(i) a target (A) for sputtering, which comprises In, Sb and O, and whoseatomic ratio of Sb/In is from 0.9 to 1.1, and

(ii) a target (B) for sputtering, which comprises Sb (the process beinghereinafter referred to as “process-1”),

(2) a process for producing an InSbO₄-containing transparentelectroconductive film, which comprises the step of sputteringsimultaneously:

(i) a target (A) for sputtering, which contains In, Sb and O, and whoseatomic ratio of Sb/In is from 0.9 to 1.1,

(ii) a target (B) for sputtering, which contains Sb, and

(iii) at least one target (C) for sputtering selected from the groupconsisting of Sn, SnO₂, Hf and HfO₂ (the process being hereinafterreferred to as “process-2”),

(3) a process for producing an InSbO₄-containing transparentelectroconductive film, which comprises the step of sputteringsimultaneously;

(i) a target CD) for sputtering, which contains In, Sb, O and at leastone element selected from the group consisting of Sn and Hf, and whoseatomic ratio of Sb/In Is from 0.9 to 1.1, and

(ii) a target (B) for sputtering, which contains Sb (the process beinghereinafter referred to as “process-3”),

(4) a transparent eletroconductive film, which contains In, Sb and O,and whose atomic ratio of Sb/In is from 0.8 to 1.5 (the film beinghereinafter referred to as “transparent electroconductive film-1”),

(5) a transparent electroconductive film, which contains In, Sb, O andat least one element selected from the group consisting of Sn and Hf,and whose atomic ratio of Sb/In is from 0.8 to 1.5 (the film beinghereinafter referred to as “transparent conductive film-2”),

(6) a target for sputtering, which contains In, Sb and O, and whoseatomic ratio of Sb/In is from 1.2 to 2.0,

(7) a target for sputtering, which contains In, Sb, O and at least oneelement selected from the group consisting of Sn and Hf, and whoseatomic ratio of Sb/In is from 1.2 to 2.0,

(8) a process for producing an InSbO₄-containing transparentelectroconductive film, which comprises the step of sputtering a target(E) for sputtering, which contains in, Sb and O, and whose atomic ratioof Sb/In is from 1.2 to 2.0 (the process being hereinafter referred toas “process-4”),

(9) a process for producing an InSbO₄-containing transparentelectroconductive film, which comprises the step of sputteringsimultaneously:

(i) a target (E) for sputtering, which contains In. Sb and O, and whoseatomic ratio of Sb/In is from 1.2 to 2.0, and

(ii) at least one target (C) for sputtering selected from the groupconsisting of Sn, SnO, Hf and HfO₂ (the process being hereinafterreferred to as “process-5”), and

(10) a process for producing an InSbO₄-containing transparentelectroconductive film, which comprises the step of sputtering a target(F) for sputtering, which contains In, Sb, O and at least one elementselected from the group consisting Sn and Hf, and whose atomic ratio ofSb/In is from 1.2 to 2.0 (the process being hereinafter referred to as“process-6”).

DETAILED DESCRIPTION OF THE INVENTION

The “target for sputtering” and “electroconductive”are hereinafterreferred to simply as “target” and “conductive”, respectively.

Among the processes for producing the transparent conductive film inaccordance with the present invention, the above-mentioned process-1 toprocess-3 are explained as follows.

In the present invention, an atomic ratio of Sb/In in the target (A)containing In. Sb and O, and that in the target (D) containing In, Sb, Oand at least one element selected from the group consisting of Sn andHf, are from 0.9 to 1.1, respectively. When the atomic ratio is lessthan 0.9 or exceeds 1.1, it may be difficult to obtain a transparentconductive film having a high conductivity. As the case maybe, thetransparent conductive film is hereinafter referred to simply as “film”.

The target (A) used in the present invention means a target containingInSbO₄, or a target containing a mixture of an indium oxide and anantimony oxide, provided that an atomic ratio of Sb/In is from 0.9 to1.1. Of these, the InSbO₄-containing target is preferred.

Similarly, the target (D) used in the present invention means a targetcontaining InSbO₄, or a target containing a mixture of an indium oxideand an antimony oxide, provided that an atomic ratio of Sb/In is from0.9 to 1.1. Of these, the InSbO₄-containing target is preferred.

In the present invention, a process using a combination of the target(D) and the target (B) containing metal Sb is more preferable than aprocess using a combination of the target (A) and the target (B),because a film having a higher conductivity can be obtained. Each of Snand Hf in the target (D) is a dopant. From a viewpoint of obtaining afilm having a high conductivity, an Sn content in the target (D), an Hfcontent in said target (D) or a total content of Sn and Hf in saidtarget (D) is preferably not more than 0.2 in terms of atomic ratio,respectively, provided that the sum of Sn, Hf, In and Sb is 1.

It is possible to dope at least one element selected from the groupconsisting of Sn and Hf even by a process comprising the step ofsputtering simultaneously the target (A), the target (B) and at leastone target (C) selected from the group consisting of Sn, SnO₂, Hf andHfO₂. Said process is more preferable than a process using a combinationof the target (A) and the target (B), because a film having a higherconductivity can be obtained. A total area of a sputtered face in thetarget (C) is preferably not more than 0.2, provided that a total areaof a sputtered face in the target (A) is 1. When the area exceeds 0.2, afilm having a higher conductivity may not be obtained. It is permittedto use a plurality of at least one kind of the target (C).

In the target (C), target (A) and target (D) used in the presentinvention, elements other than Ti, Zr, Si, Ge and Pb are impurities,provided that Sn, Hf, In, Sb and O are naturally exceptions. From aviewpoint of obtaining a film having a high conductivity, it Ispreferable to use these targets having a small content of theimpurities, preferably not more than 1% by weight, provided that theweight of the target is 100% by weight. For the purposes of improvingsurface smoothness of a film obtained, improving density thereof,improving conductivity thereof and improving a sputtering speed, each ofthe above-mentioned targets may contain at least one oxide such as Tioxides, Zr oxides, Si oxides, Ge oxides and Pb oxides.

The target (B) used In the present invention can be produced by shapingmetal Sb into a plate such as a disc like plate or a square plate, whichare preferable shapes for a target.

When the target (A) and the target (B) are not sputtered simultaneously,for example, when the step of sputtering the target (A) only and thestep of sputtering the target (B) only are alternately repeated, it maybe difficult to obtain a film having a high conductivity. Similarly,when the target (D) and the target (B) are used, or when the target (A),the target (B) and the target (C) are used, these targets are sputteredsimultaneously.

In the present invention, a ratio of an area of a sputtered face in thetarget (A) to that of a sputtered face in the target (B), and a ratio ofan area of a sputtered face in the target (D) to that of a sputteredface in the target (B) are preferably 1: 0.001 to 0.1, respectively,from a viewpoint of obtaining a film having a high conductivity. Whenmore than one target is used, the above-mentioned area means the sum ofsputtered faces in respective targets.

The target (A) used in the present invention can be produced by aprocess comprising the steps of (i) molding a mixture of an indium oxidepowder and an antimony oxide powder to obtain a molded product, and (ii)sintering the molded product. It is preferable to use a high purityindium oxide powder and a high purity antimony oxide powder, each ofwhich has a content of impurities of not more than 1% by weight.

The target (D) used in the present invention can be produced by aprocess comprising the steps of (i) molding a mixture of an indium oxidepowder, an antimony oxide powder and at least one powder selected fromthe group consisting of a tin oxide powder and a hafnium oxide powder toobtain a molded product, and (ii) sintering the molding product. It ispreferable to use each high purity powder having a content of theimpurities of not more than 1% by weight.

The indium oxide powder and the antimony oxide powder can be mixed witheach other using a mixing machine usually industrially used such as aball mill, vibrating mill, ATTRITOR (which is a trade name, and ismanufactured by Mitsui Mining Co., Ltd.) and a V-type mixing machine.The powders can also be mixed with each other according to a wet mixingmethod with use of the above-mentioned mixing machine. In case of thewet mixing, the resulting powder mixture can be dried according to adrying method such as a heat drying method, a vacuum drying method and afreeze drying method.

The dried powder mixture may be (1) molded to obtain a molded product,(2) sintered to obtain a sintered product according to a method such asa hot pressing method and a hot isostatic pressing method, or (3)calcined at 600 to 1200° C. to obtain a calcined product (such a“calcination” being hereinafter referred to as “pre-calcination”),followed by pulverization of the pre-calcined product to obtain anInSbO₄-containing pre-calcined powder, and further followed by moldingor sintering of the pre-calcined powder. Of these, the above method (3)is preferable.

The dried powder mixture may be molded by a method usually industriallyused such as a uniaxial pressing method and a isotactic pressing methodto obtain a molded product. A molding pressure is usually within a rangeof from 10 to 300 MPa. A shape of the molded product is a disk likeplate or a square plate, which are preferable shapes for a target. Adensity of the molded product is usually from 35 to 65% of a theoreticaldensity.

The sintering can be carried out using a furnace usually industriallyused such as an electric furnace or a gas furnace in anoxygen-containing atmosphere such as air under atmospheric pressure at atemperature of from 900 to 1700° C. By sintering, a sintered product,which can be used as a target, can be obtained. The sintered product canbe cut or ground to obtain a product having a desired size. The desiredsize may be obtained by cutting or grinding the molded product, whichcan be cut or ground more easily than the sintered product.

Among the target (C), (1) a target comprising at least one oxideselected from the group consisting of SnO₂ and HfO₂ can be produced by aprocess similar to the above-mentioned one, (2) a target comprising atleast one metal selected from the group consisting of Sn and Hf can beproduced by shaping the metal into a form such as a disk like plate or asquare plate, which are preferable shapes for a target, and (3) a targetcomprising at least one oxide selected from the group consisting of SnO₂and HfO₂ and at least one metal selected from the group consisting of Snand Hf can be produced by a process comprising the steps of (i)preparing a porous sintered product containing said oxide, and (ii)impregnating the porous sintered product with said molten metal.

From a viewpoint of obtaining a film having a high conductivity, theInSbO₄-containing transparent conductive film obtained according to theprocess-1 to process-3 in accordance with the present invention maycontain oxides such as Sb₂O₄, Sb₂O₅, Sb₂O₃ and In₂O₃, as far as theatomic ratio of Sb/n is within a range of from 0.8 to 1.5.

From a viewpoint of obtaining the film having a high conductivity, it ispreferable to calcine the InSbO₄-containing transparent conductive filmobtained according to the above-mentioned processes at a temperatureranging from 500 to 1100° C. The atomic ratio of Sb/In in the film aftercalcining is also within a range of from 0.8 to 1.5.

“InSbO₄” in the InSbO₄-containing transparent conductive film obtainedaccording to the process-1 to process-3 in accordance with the presentinvention means a single phase complex oxide containing In, Sb and O.The atomic ratio of Sb/In in the film is preferably from 0.8 to 1.5.

The transparent conductive film-1 and film-2 in accordance with thepresent invention are explained as follows.

The transparent conductive film in accordance with the present inventioncontains In, Sb and O, and InSbO₄ contained in the film means a singlephase complex oxide. The transparent conductive film in accordance withthe present invention may contain oxides such as Sb₂O₃, Sb₂O₄, Sb₂O₅,and In₂O₃ in addition to InSbO₄.

From a viewpoint of obtaining the film having a high conductivity, theatomic ratio of Sb/In in the film in accordance with the presentinvention is from 0.8 to 1.5.

Further, the transparent conductive film in accordance with the presentinvention contains In, Sb, O, and at least one element selected from thegroup consisting of Sn and Hf. Said film has a higher conductivity thanthat of the In, Sb and O-containing film An Sn content or an Hf contentor a total content of Sn and Hf is preferably not more than 0.2 in termsof an atomic ratio, provided that the sum of Sn, Hf, In and Sb is 1.When the content exceeds 0.2, the film having a high conductivity maynot be obtained.

In the transparent conductive film in accordance with the presentinvention, elements other than Ti, Zr, Si, Ge and Pb are impurities,provided that Sn, Hf, In, Sb and O are naturally exceptions. A totalcontent of the impurities in the film is preferably not more than 1% byweight, from a viewpoint of obtaining a transparent conductive filmhaving a high conductivity. The transparent conductive film inaccordance with the present invention may contain elements such as Ti,Zr, Si, Ge and Pb in each amount of usually not more than 1000 ppm byweight for the purposes of improving surface smoothness of the filmobtained, improving density thereof, improving conductivity thereof andimproving a sputtering speed.

Among the processes for producing the transparent conductive film inaccordance with the present invention, the process-4, process-5 andprocess-6 are explained as follows.

The atomic ratio of Sb/In in the target (E) containing In, Sb and O, andthe atomic ratio of Sb/In in the target (F) containing In, Sb, O and atleast one element selected from the group consisting of Sn and Hf, bothof which targets are used in the present invention, are from 1.2 to 2.0,preferably from 1.3 to 1.8, and more preferably from 1.4 to 1.7.

Each composition of the target (E) and the target (F) may be (1) InSbO₄,(2) a mixture of an indium oxide such as In₂O₃ and an antimony oxidesuch as Sb₂O₃, Sb₂O₄ or Sb₂O₅, or (3) a mixture of InSbO₄ and at leastone oxide selected from the group consisting of indium oxides andantimony oxides. Of these, preferred are those containing InSbO₄ such asthe embodiments (1) and (3).

From a viewpoint of obtaining a film having a high conductivity, it ispreferable to use the target (F) rather than the target (E). Each of theelements, Sn and Hf, in the target (F) is a dopant, namely, a solidsolution substance present in InSbO₄ without changing the crystalstructure of InSbO₄. From a viewpoint of obtaining a film having a highconductivity, an Sn content or an Hf content or a total content of Snand Hf is preferably not more than 0.2 in terms of an atomic ratio,provided that the sum of Sn, Hf, In and Sb is 1.

In the above-mentioned process-5, wherein the target (E) and the target(C) are sputtered simultaneously, a total area of a sputtered face inthe target (C) is preferably not more than 0.2, provided that a totalarea of a sputtered face in the target (E) is 1, from a viewpoint ofobtaining a film having a high conductivity. It is permitted to use aplurality of at least one kind of the target (C).

In the target (C), target (E) and target (P) used in the presentinvention, elements other than Ti, Zr, Si, Ge and Pb are impurities,provided that Sn, Hf, In, Sb and O are naturally exceptions. From aviewpoint of obtaining a film having a high conductivity, a content ofthe impurities in each of these targets is preferably not more than 1%by weight, provided that a weight of the target is 100% by weight. Eachof these targets may contain at least one oxide such as Ti oxides, Zroxides, Si oxides, Ge oxides and Pb oxides in an amount of usually notmore than 1000 ppm by weight in terms of the element contained in eachof said oxides, for the purposes of improving surface smoothness of thefilm obtained, improving density thereof, improving conductivity thereofand improving a sputtering speed.

The target (E) used in the present invention can be produced by aprocess comprising the steps of (i) shaping a mixture of an indium oxidepowder and an antimony oxide powder to obtain a shaped product, and (ii)sintering the shaped product. It is preferable to use each of the indiumoxide powder and the antimony oxide powder, which has a content ofimpurities of not more than 1% by weight.

The target (F) used in the present invention can be produced by aprocess comprising the steps of (i) shaping a mixture of an indium oxidepowder, an antimony oxide powder and at least one powder selected fromthe group consisting of a tin oxide powder and a hafnium oxide powder,to obtain a shaped product, and (ii) sintering the shaped product. It ispreferable to use each of the indium oxide powder, the antimony oxidepowder, the tin oxide powder and the hafnium oxide powder, which has acontent of impurities of not more than 1% by weight.

The above-mentioned powders can be mixed with one another using a mixingmachine usually industrially used such as a ball mill, a vibrating mill,ATTRITOR (which is a trade name, and is manufactured by Mitsui MiningCo., Ltd.) and a V-type mixing machine. The powders can also be mixedwith each other according to a wet mixing method with use of theabove-mentioned mixing machine. In case of the wet mixing, the resultingpowder mixture can be dried according to a drying method such as a heatdrying method, a vacuum drying method and a freeze drying method.

The dried powder mixture may be (1) molded to obtain a molded product,(2) sintered to obtain a sintered product according to a method such asa hot pressing method and a hot isostatic pressing method, or (3)calcined at 600 to 1200° C. to obtain a calcined product (such a“calcination” being hereinafter referred to as “pre-calcination”),followed by pulverization of the pre-calcined product to obtain anInSbO₄-containing pre-calcined powder, and further followed by moldingor sintering of the pre-calcined powder. Of these, the above method (3)is preferable.

The dried powder mixture may be molded by a method usually industriallyused such as a uniaxial pressing method and a isotactic pressing methodto obtain a molded product. A molding pressure is usually within a rangeof from 10 to 300 MPa. A shape of the molded product is a disk likeplate or a square plate, which are preferable shapes for a target. Adensity of the molded product is usually from 35 to 65% of a theoreticaldensity.

The sintering can be carried out using a furnace usually industriallyused such as an electric furnace or a gas furnace in anoxygen-containing atmosphere such as air under atmospheric pressure at atemperature of from 900 to 1700° C. By sintering, a sintered product,which can be used as a target, can be obtained. The sintered product canbe cut or ground to obtain a product having a desired size. The desiredsize may be obtained by cutting or grinding the molded product, whichcan be out or ground more easily than the sintered product.

Among the target (C), (1) a target comprising at least one oxideselected from the group consisting of SnO₂ and HfO₂ can be produced by aprocess similar to the above-mentioned one, (2) a target comprising atleast one metal selected from the group consisting of Sn and Hf can beproduced by shaping the metal into a form such as a disk like plate or asquare plate, which are preferable shapes for a target, and (3) a targetcomprising at least one oxide selected from the group consisting of SnO₂and HfO₂ and at least one metal selected from the group consisting of Snand Hf can be produced by a process comprising the steps of (i)preparing a porous sintered product containing said oxide, and (ii)impregnating the porous sintered product with said molten metal.

From a viewpoint of obtaining a film having a high conductivity, theInSbO₄-containing transparent conductive film obtained according to theprocess-4 to process-6 in accordance with the present invention maycontain oxides such as Sb₂O₄, Sb₂O₅, Sb₂O₃ and In₂O₃, as far as theatomic ratio of Sb/In is within a range of from 0.8 to 1.5.

From a viewpoint of obtaining the film having a high conductivity, it ispreferable to calcine the InSbO₄-containing transparent conductive filmobtained according to the above-mentioned processes at an ultimatemaximum temperature ranging from 500 to 1100° C. When the ultimatemaximum temperature is out of the range, the conductivity may not beimproved by the calcination. The atomic ratio of Sb/In in the film aftercalcining is also within a range of from 0.0 to 1.5.

The transparent conductive films in accordance with the presentinvention r and those obtained according to the processes in accordancewith the present invention have a high conductivity, and can be used forapplications such as electrodes for inorganic EL panels, liquid crystaldisplays and solar batteries; hot wave reflection films for windowglass; and antistatic films. Particularly, the transparent conductivefilms exhibiting little decrease in conductivity when heat-treated at ahigh temperature are suitable for the inorganic EL panels.

Further, the transparent conductive films in accordance with the presentinvention and those obtained according to the processes in accordancewith the present invention nave a lower content of expensive indium thanthe film comprising the ITO, and therefore, the former films are cheaperthan the latter film.

Still further, the transparent conductive films in accordance with thepresent invention and those obtained according to the processes inaccordance with the present Invention have little absorption of lightranging from visible rays having short wave lengths to ultraviolet rays.Therefore, their transmittance of visible rays is so high that theirtransparency is satisfactory.

EXAMPLE

Examples of the present invention are given as follows, but the presentinvention is not limited thereto.

Example 1

An indium oxide powder (In₂O₃ powder) having a purity of 99.99%,manufactured by Kojundo Chemical Laboratory Co., Ltd. and an antimonyoxide powder (Sb₂O₃ powder) having a high purity ceramics grademanufactured by Junsei Chemical Co., Ltd. were weighed so as to make anatomic ratio of Sb/In=1. Both powders were mixed in the presence ofethanol according to a wet ball milling method with use of zirconiaballs having a diameter of 5 mm to obtain a slurry.

The slurry was heated to remove ethanol, and the residue waspre-calcined in air atmosphere at 700° C. for 5 hours in an aluminacrucible to obtain a pre-calcined powder. The pre-calcined powder wasfound to be a mixture of Sb₂O₄ (JCPDS Card No. 110694), In₂O₃ (JCPDSCard No. 60416) and InSbO₄ (JCPDS Card No. 150522) according to an X-raydiffraction method.

The pre-calcined powder was pulverized in the presence of ethanolaccording to a wet ball milling method with use of zirconia balls havinga diameter of 2 mm to obtain a slurry.

The slurry was heated to remove ethanol, and the residue was againdispersed in ethanol. Polyvinylbutyral, a trade name of S-LEC B,manufactured by Sekisui Chemical Co. Ltd., as a binder was addedthereto, and the mixture was stirred and thereafter dried to obtain apowder.

The powder was shaped into a disc like form under pressure of 100 MPa ina mold using an uniaxial press, and the shaped product was furthershaped under pressure of 150 MPa using a CIP (Cold Isostatic Press) toobtain a disc like product.

The disc like product was sintered in An air atmosphere under anatmospheric pressure at 1000° C. for 5 hours to obtain a sinteredproduct. The sintered product (target) was found to be a mixture ofSb₂O₄, In₂O₃ and InSbO₄ according to an X-ray diffraction method.

Both targets of the sintered product and a disc of metal antimony wereset in a chamber of a sputtering apparatus, a trade name of Type L-332H,manufactured by ANELVA Co., and a silicon substrate, on which a film isto be deposited, was set in the sputtering apparatus. An area ratio ofan area of a sputtered face in the disc of metal antimony to that of asputtered face in the sintered product was found to be 0.0044. Ar gaswas introduced in the sputtering apparatus, and sputtering was carriedout under conditions of pressure of 1 Pa. electric power of 50W and asubstrate temperature of 400° C. to obtain a substrate deposited with afilm.

The substrate was calcined at 900° C. to obtain a conductive film, whichwas visually transparent. An atomic ratio of Sb/In in the obtainedtransparent conductive film was found to be 0.92, and resistivity of thefilm was found to be 6×10⁻³ Ω cm.

Example 2

The sintered product obtained in Example 1, the same disk of metalantimony as that in Example 1 and a disk of SnO₂, which were targets,and a silicon substrate as a substrate on which a film is to bedeposited were set in the sputtering apparatus used in Example 1.

Sputtering was carried out under the same conditions as those in Example1, and the resulting film was calcined at 700° C. to obtain a conductivefilm, which was visually transparent. A doping amount of Sn in theobtained transparent conductive film was found to be 4.5 atomic %, andresistivity of the film was found to be 9×10⁻³ Ω cm.

Example 3

The sintered product obtained in Example 1, the same disk of metalantimony as that in Example 1 and a disk of HfO₂, which were targets,and a silicon substrate as a substrate on which a film is to bedeposited were set in the sputtering apparatus used in Example 1.

Sputtering was carried out under the same conditions as those in Example1, and the resulting film was calcined at 700° C. to obtain a conductivefilm, which was visually transparent. A doping amount of Hf in theobtained transparent conductive film was found to be 2.4 atomic %, andresistivity of the film was found to be 5×10⁻³ Ω cm.

Comparative Example 1

The sintered product obtained in Example 1 only as a target and asilicon substrate as a substrate on which a film is to be deposited wereset in the sputtering apparatus used in Example 1.

Sputtering was carried out under the same conditions as those in Example1, and the resulting film was calcined at 700° C. to obtain a conductivefilm, which was visually transparent. An atomic ratio of Sb/In in theobtained transparent conductive film was found to be 0.67, andresistivity of the film was found to be as high as 1×10⁻³ Ω cm.

Example 4

An indium oxide powder (In₂O₃ powder) having a purity of 99.99%,manufactured by Kojundo Chemical Laboratory Co., Ltd. and an antimonyoxide powder (Sb₂O₃ powder) having a high purity ceramics grademanufactured by Junsei Chemical Co., Ltd were weighed so as to make anatomic ratio of Sb/In=1.5. Both powders were mixed in the presence ofethanol according to a wet ball milling method with use of zirconiaballs having a diameter of 5 mm to obtain a slurry.

The slurry was heated to remove ethanol, and the residue waspre-calcined in air atmosphere at 700° C. for 5 hours in an aluminacrucible to obtain a pre-calcined powder. The pre-calcined powder wasfound to be a mixture of Sb₂O₄ (JCPDS Card No. 110694), In₂O₃ (JCPDSCard No. 60416) and InSbO₄ (JCPDS Card No. 150522) according to an X-raydiffraction method.

The pre-calcined powder was pulverized in the presence of ethanolaccording to a wet ball milling method with use of zirconia balls havinga diameter of 2 mm to obtain a slurry.

The slurry was heated to remove ethanol, and the residue was againdispersed in ethanol. Polyvinylbutyral, a trade name of S-LEC B,manufactured by Sekisui Chemical Co. Ltd. as a binder was added thereto,and the mixture was stirred and thereafter dried to obtain a powder.

The powder was shaped into a disc like form under pressure of 100 MPa ina mold using an uniaxial press, and the shaped product was furthershaped under pressure of 150 MPa using a CIP (Cold Isostatic Press) toobtain a disc like product.

The disc like product was sintered in an air atmosphere under anatmospheric pressure at 1000° C. for 5 hours to obtain a sinteredproduct. The sintered product (target) was found to be a mixture ofSb₂O₄, In₂O₃ and InSbO₄ according to an X-ray diffraction method.

Both the sintered product as a target and a silicon substrate on which afilm is to be deposited were set in the sputtering apparatus used inExample 1. A mixed gas of 60% by volume of oxygen and 40% by volume ofargon was introduced in the sputtering apparatus. Sputtering was carriedout under conditions of pressure of 1 Pa, electric power of 50 W and asubstrate temperature of 400° C., and thereafter, the film deposited onthe substrate was calcined at 900° C. to obtain a conductive film, whichwas visually transparent. An atomic ratio of Sb/In in the obtainedtransparent conductive film was found to be 1.13, and resistivity of thefilm was found to be 7×10⁻³ Ω cm.

The substrate on which the film was deposited was heat-treated at 700°C., 900° C., 1000° C. and 1100° C., respectively. Respective filmsobtained were visually transparent, and their resistivity was found tobe 2×10⁻² Ω cm, 7×10⁻³ Ω cm, 9×10⁻³ Ω cm and 1×10⁻² Ω cm, respectively.

Example 5

The sintered product obtained in Example 4 and a disk of SnO₂, both ofwhich were targets, and a silicon substrate as a substrate on which afilm is to be deposited were set in the sputtering apparatus used inExample 1.

Sputtering was carried out under the same conditions as those in Example4 to obtain a conductive film, which was visually transparent. A dopingamount of Sn in the obtained transparent conductive film was found to be7.0 atomic %, and resistivity of the film was found to be 9×10⁻³ Ω cm.

Example 6

The sintered product obtained in. Example 4 and a disk of HfO₂, both ofwhich were targets, and a silicon substrate as a substrate on which afilm is to be deposited were set in the sputtering apparatus used inExample 1.

Sputtering was carried out under the same conditions as those in Example4, and the resulting film was calcined at 900° C. to obtain a conductivefilm, which was visually transparent. A doping amount of Hf in theobtained transparent conductive film was found to be 3.0 atomic %, andresistivity of the film was found to be 1×10⁻³ Ω cm.

What is claimed is:
 1. A transparent electroconductive film, whichcontains In, Sb and O, and whose atomic ratio of Sb/In is from 0.8 to1.5.
 2. A transparent electroconductive film, which contains In, Sb, Oand at least one element selected from the group consisting of Sn andHf, and whose atomic ratio of Sb/In is from 0.8 to 1.5 and Sn content oran Hf content or a total content of Sn and Hf is not more than 0.2 interms of an atomatic ratio, provided that the sum of Sn, Hf, In and Sbis 1.